DE3400851A1 - AQUEOUS VOLCANIZATION ADHESIVE - Google Patents

Abstract

1. An aqueous binder dispersion for the vulcanization of rubber onto substrates stable under vulcanization conditions, consisting of a halogen-containing polymer in latex form polyfunctional aromatic nitroso compounds masked polyfunctional isocyanates pigments, carbon black, foam inhibitors, emulsifiers and other auxiliaries, characterized in that the halogenated polymer is a copolymer of a halogenated conjugated diene, an alkylating monoalkenyl aromatic alkyl halite and, if desired, an unsaturated carboxylic acid and other standard additives are present as thickeners and, if desired auxiliairies.

Description

Henkelstrasse 67 '^' HENKELKGaA

4000 Düsseldorf, 9.1.1984 ZR-FE / Patents

Dr. Wi / Br

Patent application

D 6958
"Aqueous vulcanization adhesive"

The invention relates to an improved aqueous binder for vulcanizing different Rubber types on vulcanization-stable substrates.

With vulcanization adhesives there is now an increasing desire to have products available that are used in the Processing emit as small amounts of harmful and flammable substances as possible. It has therefore been since For some time efforts have been made to replace solvents with water. In the European patent O 021186 proposed by the applicant, such an aqueous binder made of homo- and / or copolymers of vinylidene chloride and / or butadiene-acrylonitrile copolymers, aromatic nitroso compounds, blocked isocyanates, Polyvinylpyrrolidone and various auxiliaries build up. Although these products have proven themselves, there was still a desire to improve the bond strength compared to polar rubber types, such as nitrile rubber, and improve the economy the binder further 'to increase.

The object of the invention is therefore to provide an improved aqueous binder for vulcanizing rubber to create vulcanization-stable substrates, which is used for both polar and non-polar rubber types can be. Another object of the invention is to provide a binder that is due to its consistency already at comparatively

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low active substance content gives favorable results.

The invention thus relates to an aqueous binder dispersion for vulcanizing rubber onto substrates that are stable under vulcanization conditions, consisting of

- a halogen-containing polymer in latex form

- multifunctional aromatic nitroso compounds

- disguised multifunctional isocyanates

TO - pigments, carbon black, defoamers, emulsifiers and

- other auxiliary materials,

characterized in that the halogenated polymer is a copolymer

- a halogenated conjugated diene

- an alkylating monoalkenyl aromatic alkyl halite

- and, if desired, an unsaturated carboxylic acid acts

and, as auxiliaries, thickeners and, if desired, other customary additives available.

The invention also relates to the use of the aqueous binder dispersions for vulcanization of polar and / or non-polar rubber mixtures on substrates that are stable to vulcanization, in particular Metals or aramid fibers.

The aqueous binder dispersions according to the invention is based on a halogenated copolymer in latex form as the most important component in terms of quantity. Included the copolymer consists of two and, if desired, three types of monomers, namely halogenated ones

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conjugated dienes, alkylating monoalkenyl aromatic alkyl halides and, if desired, unsaturated carboxylic acids. Copolymers of the first two Types of monomers are already known in the art addressed. Their manufacture and use in adhesives is already described in the German Offenlegungsschrift 31 25 286. From the mentioned However, it does not appear from the published patent application that particularly favorable results when using unsaturated carboxylic acids for the preparation of the copolymer can be achieved and that such copolymers in an advantageous manner with blocked polyfunctional Isocyanates can be combined according to the invention.

As halogenated conjugated dienes for the preparation of the halogenated ones used in the binders according to the invention Polymers, halogenated butadienes and / or isoprenes can be used. Here is the Use of chlorinated substances is preferred, in particular the compounds 2-chloro-1,3-butadiene and 2,3-dichloro-1,3-butadiene are preferred.

The halogenated polymers used in the binders according to the invention also contain monoalkenyl aromatic alkyl halides. Examples of such compounds are vinylbenzyl chloride (p-chloromethylvinylbenzene), p-trichloromethylvinylbenzene, ρ (v ^ -chloroethyl) -vinylbenzene, p- (dt-chlorobutyl) -vinylbenzene; cL -chlorovinylbenzyl chloride; o, m-di (<k-chloroethyl) vinylbenzene; 4-chloromethylvinylnaphthalene, the corresponding bromine and iodine analogs, and the like. Presently, vinylbenzyl chloride is preferred as the monoalkenyl aromatic alkyl halide.

In the production of the halogenated polymers on which the binders according to the invention are based, it is preferable

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also use unsaturated acids. Suitable unsaturated acids are, for example, acrylic acid, methacrylic acid, Itaconic acid, crotonic acid, maleic acid and / or fumaric acid.

When producing a halogenated polymer that does not contain any unsaturated carboxylic acids, has a proportion of halogenated dienes from 67 to 97 percent by weight, preferably from 75 to 97, in particular proven from 92 to 97. In contrast, one goes in the production of the tert. Polymers, so the halogenated polymers with the concomitant use of unsaturated acids from 30 to 96 percent by weight, preferably from 70 to 96 weight percent halogenated dienes, 2 to 32 weight percent, preferably 2 to Weight percent alkylating monoalkenyl aromatic alkyl halides and 2 to 50 weight percent, preferably 1 to 10 percent by weight unsaturated acids. Halogenated polymers with particularly favorable Properties can be derived from 2,3-dichloro-1,3-butadiene (for example 92 to 96 weight percent) vinylbenzyl chloride (2.5 to 4 weight percent) and Prepare acrylic acid (3 to 4 percent by weight).

The production of such halogenated copolymers in latex form is already known. For copolymers from halogenated dienes and monoalkenyl aromatic alkyl halides is as mentioned in the opening paragraph German Offenlegungsschrift 31 25 286 described. Copolymers which also contain polymerizable acids can be prepared analogously. In detail The specialist knowledge of polymer chemistry in the field of emulsion polymerization of ethylenically unsaturated applies here Links. So the latices contain the

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halogenated polymers the usual substances such as emulsifiers and / or protective colloids. The fixed salary of these latices is between 30 and 60 percent by weight.

The proportion of the halogenated polymers in the dry substance of the binder is 30 to 70, preferably 50 to 60 percent by weight.

The aqueous binders according to the invention contain polyfunctional aromatic nitroso compounds as a further important component. These are derivatives of benzene, naphthalene, anthracene and / or biphenyl with at least 2 nitroso groups, which are preferably not bound to directly adjacent ring carbon atoms. Particularly preferred here are aromatic dinitroso compounds, for example dinitrosobenzenes or dinitrosonaphthalenes, among these the meta- and para-compounds. The ', polyfunctional aromatic nitroso compounds can have any other substituents, for example alkyl groups, in addition to the nitroso groups.

Examples of aromatic nitroso compounds are: m-di-nitrosobenzene, p-di-nitrosobenzene, m-di-nitrosonaphthalenes, p-di-nitrosonaphthalene, 2,5-di-nitrosop-cymol, 2-methyl-1,4-di-nitrosobenzene, 2-methyl-5-chloro-1,4-dinitrosobenzene, 2-fluoro-1,4-dinitrosobenzene, 2-methoxy-1,3-dinitrosobenzene, 5-chloro-1,3-dinitrosobenzene, 2-benzyl-1,4-dinitrosobenzene and 2-cyclo-, hexyl-1,4-dinitrosobenzene.

The multifunctional aromatic nitroso compounds are on the dry substance of the aqueous binder involved with 15 to 25 percent by weight. In the manufacture of the binders, preference is given to the nitroso compounds not to be used as such, i.e. in chemically pure form, but in suspensions assume, especially suspensions in water.

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Such suspensions are commercially available.

The aqueous binders according to the invention contain a thickener as a further component. Although you can here also organic thickeners such as xanthan, cellulose ethers, polyacrylamide or Copolymers of acrylic acid and its esters can be used, but inorganic thickeners are preferred. A very particularly preferred thickening agent is silicon dioxide in finely powdered form with a large surface. Such types of silicon dioxide suitable for thickening purposes are generally known and commercially available. A suitable product is, for example, under the brand name Aerosil Company Degussa AG distributed. The proportion of the thickener in the dry substance of the binder is 2 to 10 percent by weight, preferably 5 to 8 percent by weight. When using, especially the preferred Thickeners, aqueous binder dispersions are formed due to their increased viscosity Do not knock it away before drying and hardening and therefore it allows cheap with a low active substance content Achieve results. The thickeners can be used as such in the aqueous binder dispersions be introduced or stirred in. However, it is preferred to use a pre-solution or in the case of the thickener Prepare a silicon dioxide-based predispersion and this with the other liquid ingredients to mix.

The aqueous binders according to the invention contain blocked isocyanates as a further important component.

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These are derived from the commercially available isocyanates, which can be used in a variety of ways, for example of tolylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dimerized tolylene diisocyanate, hexamethylene diisocyanate and others more such as multifunctional isocyanates such as triphenyl methane triisocyanate or the addition product of 3 mol of tolylene diisocyanate with 1 mol of trimethylolpropane. As a means for example, phenols, alcohols, such as tert. Amyl alcohol or tert. Butanol, acetoacetic ester, malonic ester, acetylacetone, butanone oxime, phthalimide, imidazole or sodium hydrogen .

A particularly preferred product is the adduct of an epoxidized novolak (epoxy number 24, epoxy value 56) with diphenylmethane diisocyanate in a molar ratio of 1: 3, capped with butanone oxime. The production of such Products is known. It is made in a simple manner by combining epoxy and diisocyanate and subsequent heating to temperatures up to 80 carried out. The multifunctional isocyanate thus obtained is then capped in a known manner with butanone oxime. The blocked isocyanate adduct is with 3 to 10, preferably 4 to 7 percent by weight of the solids content of the aqueous agent.

The dispersions according to the invention can also contain customary adhesion-improving fillers. There are in particular carbon black in amounts of 2 to percent by weight, zinc oxide in amounts of 0.1 to 2 percent by weight each based on dry binder or basic lead phosphite and the like in Question. Pigments can also be incorporated.

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Contain those according to the invention as further constituents aqueous binders, emulsifiers in amounts of 1 to 8 percent by weight. Anionic or nonionic emulsifiers are suitable here, e.g. the adducts of Ethylene oxide on alkylphenols such as nonylphenol or on fatty alcohols and sulfonation products of this type Adducts. Stabilizers can also be used. Here are water-soluble colloids, such as Cellulose ethers or polyvinyl alcohol are suitable. Defoamers can also be used. The amount is preferably 0.01 to 0.6 percent by weight.

The solids content of the aqueous binders according to the invention is chosen by the person skilled in the art so that the ί

desired consistency is maintained. Typically the solids content is 10-30%, in particular 15-25% by weight.

The aqueous binders according to the invention are suitable for connecting vulcanizable elastomers with a Variety of substrates, for example with numerous metals such as iron, stainless steel, lead, aluminum, Copper, brass, bronze, monel metals, nickel, zinc and the like .. They are also suitable for treated Metals such as phosphated steel, galvanized steel and can also be used in glass and ceramic materials as well as for high-melting plastics such as aramid fibers. It should be emphasized the favorable effect, especially when vulcanizing polar rubbers, e.g. nitrile rubber on araiuid fibers or metals.

The binary means are applied to the substrate surfaces in a conventional manner Way, such as by dipping, spraying, brushing and the like. Applied. May be it is advisable to carry out a pretreatment with an adhesion-improving agent (primer) made of chlorinated rubber,

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Phenolic resin or the like. Perform. The substrate surfaces are allowed to dry after coating, before they are brought together. After the surfaces have been put together, the composite structures become heated in a conventional manner to cause vulcanization.

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Examples

Manufacture of rubber compounds

In the following examples, the rubber compounds designated A, B, C, D and E were applied to substrates vulcanized. The following are first the compositions of the mixtures and the vulcanization conditions.

Mixture A (NBR)

Nitrile rubber (42% acrylonitrile) 100.0 parts by weight

Stearic acid 1.0 "

Zinc oxide 5.0 "

Dibutyl phthalate 10.0 "

SFR carbon black 65.0 "

Terpene resin 10.0 "

Tetramethylthiuram disulfide 0.31 "

sulfur 1.0 "

Vulcanization conditions: 15 min at 160 ° C

Mixture B (NBR)

Nitrile rubber (38% acrylonitrile) 100.0 parts by weight stearic acid 1.0 "

ZnO 3.0 "

SRF carbon black 30.0 "

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Winnofil S (chalk) anti-aging agent phenyl

Vulkacit Thiuram (Tetramethylthiuramdisulfid) Vulkacit CZ (Benzothiazyl-cyclohexylsulfenamide) sulfur

Vulcanization: 5 min at 175 ⁰ C mixture C (CR)

20.0 parts by weight 2.0 "

2.5 "

0.5 "0.2"

Mixing ingredients Parts by weight Baypren 210 (2-chloro-butadiene 1.3 polymer) 100.0 ASM-PAN (phenyl-'X-naphthylamine) 1.5 Stearic acid 2.0 Sterling MT (carbon black) 100.0 Ozone wax III 1.5 sulfur 0.6 Winnofil S (chalk) 70.0 Ingralen 450 (mineral oil aromat.) 20.0 Vulkacit Thiuram MS (tetramethyl- thiuram monosulfide) 1.0 Red lead 20.0

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Mixture D (CSM)

chlorosulfonated polyethylene Tego smoothness (lead oxide) ECC Devolite (aluminum silicate) Durex O (carbon black) Ingraplast S (mineral oil) NBC (nickel dibutyldithiocarbamate) Vulkacit DM (dibenzothiazole disulfide) Tetrone A (dipentamethylene thiuram tetrasulfide

100.0 parts by weight

25.0 "

80.0 "

30.0 "

35.0 "

0.5 "

0.5 "

2.0 "

Mixture E (EPDM)

Keltan 812 (EPDM) 100 ZnO 5 Stearic acid 2 Soot FEF 90 Sillitin N (silica) 55 Sunpar 2230 (mineral oil) 70 Ca 0 (surface with fatty acid treated) 6th vaseline 5 Royalac 133 (dithiocarbamate / Thiazole mixture 1 Vulkacit Mercapto (Mercaptobenz- thiazole 1, 25 DPTT (dipentamethylene thiuram tetrasulfide 1 P extra N (zinc-ethylphenyldi- thiocarbamate) 1.9 Sulfasan R (dithiodimorpholine) 1 Schv / cf el 0.5

Claims (10)

Claims 1. Aqueous binder dispersion for vulcanization from rubber to lower vulcanization stable substrates consisting of - a halogen-containing polymer in latex form - multifunctional aromatic nitroso compounds - disguised multifunctional isocyanates - Pigments, carbon black, defoamers, emulsifiers and - other auxiliary materials, characterized in that the halogenated polymer is a copolymer - a halogenated conjugated diene - an alkylating Mcnoalkenyl-aromatic-Alkylhalogenit - and, if desired, an unsaturated carboxylic acid acts and, as auxiliaries, thickeners and, if desired, other customary additives available. 2. Aqueous binder dispersion according to claim 1, characterized in that it is the halogenated Copolymers to a copolymer of halogenated butadiene and / or isoprene with a polymerizable benzyl halide and with an unsaturated carboxylic acid. 3. Aqueous binder dispersions according to the claims 1 and 2, characterized in that the halogenated copolymer of 30 to 96 percent by weight halogenated Butadiene, preferably 2,3-dichloro-1,3-butadiene 2 to 32 percent by weight of polymerizable benzyl Patent application D 6958 "& 'HENKELKGaA ZR-FE / patents halide, preferably vinylbenzyl chloride and 1 to 10 percent by weight acrylic acid and / or Methacrylic acid. 4. Aqueous binder dispersions according to Claims 1 to 3, characterized in that as a thickener an inorganic thickener, especially a finely divided silicon dioxide large inner surface is included. 5. Aqueous binder dispersions according to Claims 1 to 4, characterized in that the proportion of the halogenated polymer on the dry substance of the binder 30 to 70, preferably 50 to 60 Weight percent is. 6. Aqueous binder dispersions according to Claims 1 to 5, characterized in that the proportion of the thickener on the dry substance of the binder 2 to 10, preferably 5 to 8 percent by weight amounts to. 7. Aqueous binder dispersions according to the claims 1 to 6, characterized in that the proportion of the blocked isocyanate adducts in the dry substance of the binder is 3 to 10, preferably 4 to 7 percent by weight and that as blocked Isocyanate adducts, preferably reaction products of epoxidized novolaks (epoxy number 24, epoxy value 56) with diphenylmethane diisocyanate in a molar ratio of 1: 3, capped with butanone oxime. Patent application D 6958 · 3- HENKELKGaA ZR-FE / patents 8. Aqueous binder dispersions according to the claims 1 to 7, characterized in that 0.1 to 2 percent by weight of zinc oxide, 2 to 10 percent by weight carbon black, 1 to 8 percent by weight emulsifiers, 0.01 to 0.6 percent by weight Defoamers and, if desired, other additives are included. 9. Aqueous binder dispersions according to the claims 1 to 8, characterized in that they have a solids content of 10 to 30 percent by weight, preferably from 15 to 25 percent by weight. 10. Use of the aqueous binder dispersions according to Claims 1 to 9 for vulcanization of polar and / or non-polar rubber mixtures on substrates that are stable to vulcanization, in particular Metals or araniid fibers.